EP2300421A1 - Verfahren zur sulfonylierung einer hydroxylierten organischen verbindung - Google Patents

Verfahren zur sulfonylierung einer hydroxylierten organischen verbindung

Info

Publication number
EP2300421A1
EP2300421A1 EP09753936A EP09753936A EP2300421A1 EP 2300421 A1 EP2300421 A1 EP 2300421A1 EP 09753936 A EP09753936 A EP 09753936A EP 09753936 A EP09753936 A EP 09753936A EP 2300421 A1 EP2300421 A1 EP 2300421A1
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EP
European Patent Office
Prior art keywords
process according
formula
organic compound
group
agent
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP09753936A
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English (en)
French (fr)
Other versions
EP2300421B1 (de
Inventor
François Metz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Operations SAS
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Rhodia Operations SAS
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Publication of EP2300421A1 publication Critical patent/EP2300421A1/de
Application granted granted Critical
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Not-in-force legal-status Critical Current
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
    • C07C303/28—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reaction of hydroxy compounds with sulfonic acids or derivatives thereof

Definitions

  • the present invention relates to a process for the sulfonylation of a hydroxylated organic compound.
  • the invention relates more particularly to a trifluoromethanesulfonylation process of a hydroxylated organic compound.
  • the invention relates in particular to hydroxylated compounds of aliphatic type and more particularly those which comprise a perfluorinated aliphatic chain.
  • the invention is preferably applied to perfluorinated aliphatic alcohols and, in particular, to 2,2,2-thfluoroethanol.
  • Lewis acid is a compound comprising a metal or metalloid cation considered “intermediate" in the classification
  • Antimony chloride is an example of a Lewis acid suitable for the process described in EP-A-1 322 601.
  • the object of the present invention is to provide a method for avoiding the aforementioned drawbacks.
  • the invention relates to a trifluoromethanesulfonylation process of a hydroxylated organic compound, characterized in that it comprises the reaction of said compound, with a trifluoromethanesulfonylation agent, in an organic medium and in the presence of a heterogeneous mineral base. .
  • hydroxylated organic compound which is involved in the process of the invention more particularly corresponds to formula (I):
  • R 1 represents a hydrocarbon group, substituted or unsubstituted, comprising from 1 to 40 carbon atoms, which may be a saturated or unsaturated, linear or branched acyclic aliphatic group; a saturated, unsaturated or aromatic, monocyclic or polycyclic carbocyclic or heterocyclic group; a sequence of the aforementioned groups.
  • R 1 represents a hydrocarbon group having from 1 to
  • 20 carbon atoms which may be a saturated or unsaturated, linear or branched acyclic aliphatic group; a saturated, unsaturated or aromatic, monocyclic or polycyclic carbocyclic or heterocyclic group; a saturated or unsaturated, linear or branched, aliphatic group carrying a cyclic substituent.
  • R 1 preferably represents a linear or branched saturated acyclic aliphatic group preferably having from 1 to 12 carbon atoms, and even more preferably from 1 to 4 carbon atoms.
  • the invention does not exclude the presence of unsaturation on the hydrocarbon chain such as one or more double bonds which may or may not be conjugated, or a triple bond.
  • the hydrocarbon chain may be optionally interrupted by a heteroatom (for example, oxygen or sulfur) or by a functional group to the extent that it does not react and there may be mentioned in particular a group such as in particular -CO-.
  • the hydrocarbon chain may optionally carry one or more substituents (for example, halogen, ester, aldehyde) insofar as they do not interfere with the sulfonylation reaction.
  • substituents for example, halogen, ester, aldehyde
  • the hydrocarbon chain preferably carries one or more fluorine atoms.
  • the acyclic aliphatic group, saturated or unsaturated, linear or branched may optionally carry a cyclic substituent.
  • ring is meant a carbocyclic or heterocyclic ring, saturated, unsaturated or aromatic.
  • the acyclic aliphatic group may be linked to the ring by a valency bond, a heteroatom or a functional group such as oxy, carbonyl, carboxy, sulfonyl etc.
  • cyclic substituents it is possible to envisage cycloaliphatic, aromatic or heterocyclic, in particular cycloaliphatic, substituents comprising 6 ring carbon atoms or benzenes, these cyclic substituents being themselves optionally carrying any substituent insofar as they do not do not interfere with the reactions involved in the process of the invention.
  • alkyl or alkoxy groups having 1 to 4 carbon atoms may be mentioned.
  • aliphatic groups bearing a cyclic substituent more particularly aralkyl groups having 7 to 12 carbon atoms, especially benzyl or phenylethyl.
  • R 1 may also represent a saturated or unsaturated carbocyclic group preferably having 5 or 6 carbon atoms in the ring; a heterocyclic group, saturated or unsaturated, in particular containing 5 or 6 atoms in the ring, including 1 or 2 heteroatoms such as nitrogen, sulfur and oxygen atoms; an aromatic or monocyclic aromatic carbocyclic or heterocyclic group, preferably phenyl or pyridyl or fused or unsubstituted polycyclic, preferably naphthyl. Since Ri comprises a cycle, it can also be substituted. The number of substituents is generally at most 4 per cycle, but most often equal to 1 or 2.
  • substituents are indifferent insofar as it does not react under the conditions of the invention, in particular with a strong base.
  • substituents that may be mentioned include alkyl groups, alkoxy groups having from 1 to 4 carbon atoms or halogen atoms.
  • the invention does not exclude the case where the hydroxylated organic compound is difunctional that is to say that it carries another OH group carried by an aliphatic chain or as a substitute of an aromatic ring.
  • the hydroxylated organic compound is difunctional that is to say that it carries another OH group carried by an aliphatic chain or as a substitute of an aromatic ring.
  • R 1 is preferably a linear or branched alkyl group having from 1 to 12 carbon atoms, and preferably from 1 to 4 carbon atoms.
  • the process of the invention is particularly applicable to aliphatic alcohols and more particularly to fluorinated and perfluorinated alcohols corresponding to formula (Ia):
  • R 1 represents a fluorinated or perfluorinated alkyl chain comprising from 1 to 10 carbon atoms and from 1 to 21 fluorine atoms, preferably from 3 to 21 fluorine atoms .
  • the invention relates more particularly to perfluorinated aliphatic alcohols corresponding to formula (Ia) in which R 1 represents a perfluorinated alkyl chain comprising from 1 to 10 carbon atoms and from 3 to 21 fluorine atoms.
  • the process of the invention is particularly applicable to compounds of formula (I) or (la) such as ethanol, 2,2,2-trifluoroethanol, 2,2-difluoroethanol or 1,1-difluoroethanol pentafluoroethanol, hexafluoroisopropanol, pentafluorophenol, p-nitrophenol, p-trifluoromethylphenol.
  • compounds of formula (I) or (la) such as ethanol, 2,2,2-trifluoroethanol, 2,2-difluoroethanol or 1,1-difluoroethanol pentafluoroethanol, hexafluoroisopropanol, pentafluorophenol, p-nitrophenol, p-trifluoromethylphenol.
  • the sulfonylating agent it is a halide of a perfluoroalkylsulfonic acid.
  • R2 represents an Rf-type perfluoroalkyl hydrocarbon group having from 1 to 10 carbon atoms
  • Z represents a fluorine, chlorine or bromine atom.
  • formula (II) the case where Z is a chlorine or bromine atom is preferably chosen.
  • Z is more preferably a bromine atom.
  • p is a number ranging from 1 to 8 and b is a number from 3 to 17.
  • the preferred sulphonylating agents have the formula (II) in which the group -SO 2 -R 2 represents: a trifluoromethanesulfonyl (triflyl) -SO 2 -FC 3 group,
  • the group R f is more preferably a CF 3 group or a CF 2 - CF 3 group .
  • trifluoromethanesulfonylation agent corresponds to the formula (II) in which R 2 represents a CF 3 group and Z represents a fluorine, chlorine or bromine atom.
  • R 2 represents a CF 3 group
  • Z represents a fluorine, chlorine or bromine atom.
  • trifluoromethanesulfonyl fluoride trifluoromethanesulfonyl chloride or trifluoromethanesulfonyl bromide.
  • Trifluoromethanesulfonyl bromide is preferred.
  • the reaction between the hydroxylated organic compound and the sulfonylating agent is conducted in the liquid phase, in the presence of an organic solvent and a base.
  • the ratio between the number of moles of sulfonylating agent and the number of moles of hydroxylated organic compound can vary between 0.5 and 2, and is preferably between 0.8 and 1.2.
  • a base whose function is to trap the halohydrogenic acid formed by the reaction.
  • An ammonium hydroxide or a monovalent metal and / or a divalent metal, preferably an alkali metal and / or alkaline earth metal may be used. More specific examples of bases to use include an alkali metal hydroxide such as sodium, potassium or cesium and an alkaline earth metal hydroxide such as magnesium, calcium, barium; a hydroxide of a group MB metal such as zinc.
  • alkali metal hydroxide such as sodium, potassium or cesium and an alkaline earth metal hydroxide such as magnesium, calcium, barium
  • a hydroxide of a group MB metal such as zinc.
  • sodium or potassium hydroxide is preferably chosen.
  • Another class of bases that can be used in the process of the invention is the carbonates and hydrogen carbonates of the alkali or alkaline earth metals.
  • Sodium or potassium carbonate is more preferably chosen.
  • the base is used in a solid form, generally in the form of a powder and more particularly in a ground form in the case of alkali or alkaline earth metal hydroxides, in particular in the case of hydroxides of sodium, potassium and lithium.
  • the grinding operation of the base can be carried out in any type of crusher resistant to corrosion of the base (for example stainless steel).
  • the amount of base used is such that the ratio between the number of moles of base and the number of moles of sulfonylating agent preferably varies between 1 and 2, and more preferably between 1, 4 and 1, 6.
  • the reaction is conducted in the presence of an organic solvent.
  • a solvent is chosen which is inert under the reaction conditions.
  • Suitable solvents are apolar organic solvents such as aliphatic, cycloaliphatic or aromatic halogenated or non-halogenated hydrocarbons or more polar organic solvents such as, in particular, ether-oxides, nitriles.
  • aliphatic and cycloaliphatic hydrocarbons more particularly paraffins, such as, in particular, hexane, heptane, octane, isooctane, nonane, decane undecane, tetradecane, petroleum ether and cyclohexane; aromatic hydrocarbons such as, in particular, benzene, toluene, xylenes, ethylbenzene, diethylbenzenes, trimethylbenzenes, cumene, pseudocumene, petroleum fractions consisting of a mixture of alkylbenzenes, especially Solvesso® type cuts.
  • paraffins such as, in particular, hexane, heptane, octane, isooctane, nonane, decane undecane, tetradecane, petroleum ether and cyclohexane
  • aromatic hydrocarbons such as, in particular, benzene
  • perchlorinated hydrocarbons such as in particular trichloromethane, tetrachlorethylene; the partially chlorinated hydrocarbons such as dichloromethane, dichloroethane, tetrachloroethane, trichlorethylene, 1-chlorobutane, 1,2-dichlorobutane; monochlorobenzene, dichlorobenzenes or mixtures thereof; trifluoromethylbenzene, trifluoromethoxybenzene.
  • the ethers can also be used as solvents.
  • Examples are aliphatic, cycloaliphatic or aromatic ether-oxides and, more particularly, methyl-tert-butyl ether, dipentyl ether, diisopentyl ether and ethylene glycol dimethyl ether (or 1,2-dimethoxyethane). ), dimethyl ether diethylene glycol (or 1,5-dimethoxy-3-oxapentane) or cyclic ethers, for example, dioxane, tetrahydrofuran.
  • nitrile solvent Mention may in particular be made of alpha or aromatic nitrites, preferably acetonitrile, propionitrile, butanenitrile, isobutanenitrile, pentanenitrile, 2-methylglutaronithl, adiponitrile, benzonitrile, tolunitrile, malonitrile, 1, 4-benzonitrile.
  • the yield of the sulfonylation reaction carried out in the presence of a heterogeneous mineral base was particularly high when an organic solvent was used.
  • nonpolar Apolar organic solvents are preferably used in the process of the invention.
  • the preferred solvents for carrying out the process of the invention are xylenes, chlorobenzene and dichlorobenzenes or mixtures thereof. It is also possible to use a mixture of organic solvents.
  • the amount of organic solvent used is preferably chosen such that the weight concentration of the sulfonylating agent in the solvent is between 5 and 50%, preferably between 20 and 40%. According to a preferred variant of the process of the invention, it is chosen to work under anhydrous conditions. However, it is possible to tolerate in the reaction medium a small amount of water, preferably less than 1% by weight and more preferably less than 0.5% by weight.
  • the reaction is generally carried out at a temperature of between 0 ° C. and the reflux temperature of the organic solvent, preferably at a temperature of between 15 ° C. and 30 ° C.
  • the sulfonylation reaction is generally carried out under atmospheric pressure but preferably under a controlled atmosphere of inert gases. It is possible to establish an atmosphere of rare gases, preferably argon, but it is more economical to use nitrogen. A pressure slightly above or below atmospheric pressure may be suitable.
  • the method of the invention is simple to implement.
  • Reagents can be introduced in many variations but some are preferred.
  • a first embodiment consists in preparing a foot consisting of the hydroxylated organic compound and the mineral base and then progressively introducing, preferably by casting, the sulphonylation agent introduced into the organic solvent.
  • Another embodiment which has the advantage of facilitating the stirring of the reaction medium is to form a foot comprising the mineral base and the organic solvent and then gradually introduce, preferably by co-casting, the agent of the reaction medium. sulfonylation and the hydroxylated organic compound.
  • the product obtained is recovered in a conventional manner. Generally, water is added which makes it possible to recover in the aqueous phase the salts formed. The aqueous and organic phases are separated. The organic phase is collected and optionally washed. The sulphonic ester is recovered from the organic phase according to conventionally used techniques.
  • distillation or extraction can be carried out with the aid of an organic solvent chosen so that it does not form an azeotrope with water.
  • the process of the invention thus makes it possible to obtain the ester in a simple manner with a good yield and a good selectivity.
  • Another advantage of the process of the invention is that it makes it possible to use a bromide-type sulphonylating agent which has the characteristic of being much less volatile than a sulphonylation agent of chloride type, which is particularly advantageous for an industrial point of view.
  • Examples 1 to 5 correspond to the sulfonylation of trifluoroethanol in the presence of a heterogeneous base (solid potassium carbonate) with the exception of Example 4 in which it is an aqueous solution of potassium carbonate.
  • Example 6 relates to the sulfonylation of ethanol in the presence of a heterogeneous base.
  • Examples 7 to 10 are comparative tests in which the base is a nitrogenous organic base.
  • Example 11 relates to the sulfonylation of ethanol using trifluoromethanesulfonyl chloride in the presence of a heterogeneous base.
  • TFSCI Trifluoromethanesulfonyl chloride (trifluoryl chloride), ACN: acetonitrile,
  • the degree of conversion (TT) of the bromide or triflyl chloride corresponds to the ratio between the number of moles of bromide or trifluoryl chloride converted and the number of moles of bromide or triflyl chloride introduced.
  • the TfOTFE yield corresponds to the ratio between the number of moles of TfOTFE formed and the number of moles of bromide or triflyl chloride introduced.
  • the yield of TfOEt corresponds to the ratio between the number of moles of TfOEt (ethyl triflate) formed and the number of moles of bromide or triflyl chloride introduced.
  • the TfOTFE selectivity corresponds to the ratio between the number of moles of TfOTFE formed and the number of moles of bromide or triflin chloride transformed.
  • the resulting heterogeneous medium is stirred with the temperature T mentioned in the following table (I), then the TFSBr (7 g, 32 mmol), diluted. by TFE (3.2 g, 32 mmol) or by a solvent (7 g) is added for a time also mentioned in Table (I).
  • reaction medium is maintained at the temperature T for a time mentioned in Table (I), then the reagents and the products obtained are determined by 19 F NMR.
  • reaction medium is maintained at the temperature T for a time mentioned in Table (II), then the reagents and the products obtained by 19 F NMR are measured .
  • Example 6 is reproduced with the sole difference that TFSCI (5.35 g, 32 mmol) is used to produce the following results:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP09753936.5A 2008-05-29 2009-05-28 Verfahren zur sulfonylierung einer hydroxylierten organischen verbindung Not-in-force EP2300421B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0802943A FR2931821B1 (fr) 2008-05-29 2008-05-29 Procede de sulfonylation d'un compose organique hydroxyle.
PCT/EP2009/056554 WO2009144281A1 (fr) 2008-05-29 2009-05-28 Procede de sulfonylation d'un compose organique hydroxyle

Publications (2)

Publication Number Publication Date
EP2300421A1 true EP2300421A1 (de) 2011-03-30
EP2300421B1 EP2300421B1 (de) 2015-12-02

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EP09753936.5A Not-in-force EP2300421B1 (de) 2008-05-29 2009-05-28 Verfahren zur sulfonylierung einer hydroxylierten organischen verbindung

Country Status (7)

Country Link
US (1) US8399709B2 (de)
EP (1) EP2300421B1 (de)
JP (1) JP5596673B2 (de)
CN (1) CN102076658B (de)
FR (1) FR2931821B1 (de)
RU (1) RU2488579C2 (de)
WO (1) WO2009144281A1 (de)

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KR101516471B1 (ko) * 2010-05-19 2015-05-04 로디아 오퍼레이션스 오르쏘-치환 5-할로페놀 및 이의 합성 중간체의 제조 방법
CN103193849B (zh) * 2012-01-04 2016-05-04 连云港润众制药有限公司 一种高纯度醋酸阿比特龙的制备方法
CN109748831A (zh) * 2018-12-17 2019-05-14 南通正达农化有限公司 一种三氟甲磺酸三氟乙酯的制备方法
CN117105824A (zh) * 2023-08-26 2023-11-24 衢州市九洲化工有限公司 一种三氟甲磺酸三氟乙酯的制备方法

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Also Published As

Publication number Publication date
FR2931821B1 (fr) 2011-03-04
FR2931821A1 (fr) 2009-12-04
JP5596673B2 (ja) 2014-09-24
RU2488579C2 (ru) 2013-07-27
WO2009144281A1 (fr) 2009-12-03
RU2010154071A (ru) 2012-07-10
US20110190542A1 (en) 2011-08-04
EP2300421B1 (de) 2015-12-02
JP2011521926A (ja) 2011-07-28
US8399709B2 (en) 2013-03-19
CN102076658A (zh) 2011-05-25
CN102076658B (zh) 2013-10-30

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